WO2018161822A1 - 一种锂离子电池用水性粘结剂及其制备方法和锂离子电池极片 - Google Patents

一种锂离子电池用水性粘结剂及其制备方法和锂离子电池极片 Download PDF

Info

Publication number
WO2018161822A1
WO2018161822A1 PCT/CN2018/077446 CN2018077446W WO2018161822A1 WO 2018161822 A1 WO2018161822 A1 WO 2018161822A1 CN 2018077446 W CN2018077446 W CN 2018077446W WO 2018161822 A1 WO2018161822 A1 WO 2018161822A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
lithium ion
ion battery
aqueous binder
water
Prior art date
Application number
PCT/CN2018/077446
Other languages
English (en)
French (fr)
Inventor
刘俊
王伟华
任建国
岳敏
Original Assignee
深圳市贝特瑞新能源材料股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 深圳市贝特瑞新能源材料股份有限公司 filed Critical 深圳市贝特瑞新能源材料股份有限公司
Priority to KR1020197008899A priority Critical patent/KR102284520B1/ko
Priority to JP2019529311A priority patent/JP6877545B2/ja
Publication of WO2018161822A1 publication Critical patent/WO2018161822A1/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B11/00—Preparation of cellulose ethers
    • C08B11/02—Alkyl or cycloalkyl ethers
    • C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
    • C08B11/10—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals
    • C08B11/12—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals substituted with carboxylic radicals, e.g. carboxymethylcellulose [CMC]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
    • C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
    • C08F261/04—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/02—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to polysaccharides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure belongs to the field of lithium ion battery materials, and relates to an aqueous binder for a lithium ion battery, a preparation method thereof and a lithium ion battery pole piece.
  • lithium-ion batteries are widely used in mobile phones, computers and electric vehicles, and have great commercial value.
  • the cathode materials of commercial lithium-ion batteries are mainly oxides such as LiCoO 2 , LiMn 2 O 4 and LiFePO 4 ; the anode materials are mainly graphite, and it is difficult to satisfy due to the low theoretical capacity of graphite (372 mAh/g).
  • the development of high-capacity silicon-based materials has become a major issue in the development of lithium-ion battery technology.
  • the silicon-based material is accompanied by a larger volume expansion and contraction (up to 300%) during charge and discharge, the electrode capacity is attenuated quickly and the cycle performance is poor. Therefore, it is required to develop a binder having high bond strength and capable of uniformly dispersing expansion stress to achieve cycle stability of a high capacity negative electrode.
  • PVDF polyvinylidene fluoride
  • SBR styrene-butadiene rubber
  • PAA acrylic polymers
  • the SBR binder when the SBR binder is applied to the silicon-based composite new anode, the silicon-based volume expansion is large due to the charge-discharge cycle, and the point bond easily loses the adhesion, which deteriorates the electrical properties.
  • PAA PAA
  • the polymer because the polymer has a high glass transition temperature, is hard at normal temperature, and tends to cause the pole piece to be hard and brittle. Therefore, the binder is prone to cracking during the coating process and after cold pressing. There are many stripes, the decarburization of the edges during the cutting, and the phenomenon that the pole pieces are bent off during the winding process, and the processing performance is poor, which seriously restricts its application in the battery.
  • CN104356979A discloses a polyacrylate aqueous binder for lithium ion battery electrode material, a preparation method thereof and a lithium ion battery pole piece, which is a crosslinked high solid content polyacrylate water-based material.
  • the binder, the binder polymer molecular segment is composed of a hydrophilic segment and a lipophilic segment, and is crosslinked by a crosslinking agent into a spatial network structure.
  • the electrode pole piece made of the binder does not have the phenomenon of "dropping" during charging and discharging, and has good bonding performance to the positive and negative electrode materials of the lithium ion battery, and can suppress the graphite negative electrode material.
  • the pole piece expands, in particular, the pole piece expansion of the silicon-based material.
  • An object of the present disclosure is to provide an aqueous binder for a lithium ion battery, a method for preparing the same, and a lithium ion battery pole piece.
  • the adhesive of the present disclosure has a high adhesive force, so that the battery pole piece has strong adhesion to the aluminum foil, the pole piece is flexible, and the first Coulomb efficiency is high.
  • the present disclosure adopts the following technical solutions:
  • the present disclosure provides an aqueous binder for a lithium ion battery having the structure of Formula I:
  • the M group is a repeating unit group of a water-soluble polymer containing a hydroxyl group or a hydroxyl group and a carboxyl group
  • R 1 is a C1-C6 linear alkylene group or a branched alkylene group
  • R 2 is an amino group, a hydroxyl group or an alkane Oxyl, hydroxyalkyl or R is a C1-C6 linear alkylene group or a branched alkylene group
  • R 3 is a phenyl group or a C1-C6 linear alkyl group or a branched alkyl group
  • R 4 is a carboxyl group, an amide group, a nitrile group
  • R ' is C1-C6 straight chain alkyl or branched alkyl
  • R 5 is hydrogen or a straight-chain alkyl group of C1-C6 Or
  • the present disclosure is directed to modifying a hydroxyl group in a water-soluble polymer repeating unit group to achieve introduction of a polar side chain-containing polar group containing a polar anionic group to enhance the polymer and current collector
  • the polar action enhances the adhesion; the anionic group can be adsorbed on the surface of the particle during the dispersion of the slurry, increasing the electrostatic repulsion between the particles, thereby improving the dispersion of the electrode slurry; the flexible side chain can destroy the original molecular chain
  • the regularity reduces the hydrogen bonding between the polymer chains, thereby weakening the crystallization; the flexible side chains can also lower the glass transition temperature of the polymer, thereby enhancing the flexibility.
  • the M group is a repeating unit group from the following structure:
  • the main chain of the aqueous binder of the present disclosure is composed of Any of the constituents, for example when the M group is derived from The repeating unit group in the structure, that is, the aqueous binder backbone of the present disclosure
  • the group is a repeating unit, and the structure shown in the above formula I is obtained by modifying the hydroxyl group contained therein, wherein some of the segments have hydroxyl groups modified, but some are not modified, and some of the repeating unit segments having a hydroxyl group are retained.
  • the group is a repeating unit, and the hydroxyl group contained therein is modified to obtain a structure as shown in the above formula I, wherein some of the segments have a hydroxyl group modified, but some are not modified, and some of the repeating unit segments having a hydroxyl group are retained, and the hydroxyl group is retained.
  • the modified segment it may be that one of the hydroxyl groups in one repeating unit is modified or a plurality of hydroxyl groups may be modified; Both represent unmodified segments.
  • the C1-C6 linear alkylene group or branched alkylene group may be a linear alkylene group or a branched alkylene group of C1, C2, C3, C4, C5, C6, for example, Is -CH 2 -, -CH 2 CH 2 - or Wait.
  • the linear or branched alkyl group of C1-C6 may be a linear alkyl group or a branched alkyl group of C1, C2, C3, C4, C5, C6, and may be, for example, a methyl group. Ethyl or Wait.
  • the alkoxy group may be a methoxy group, an ethoxy group or a propoxy group or the like.
  • the hydroxyalkyl group may be a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group or the like.
  • R 1 is -CH 2 CH 2 - or
  • R 2 is amino, hydroxy, methoxy, hydroxyethyl, hydroxypropyl,
  • R 3 is phenyl or methyl.
  • R 4 is a carboxyl group, an amide group, a nitrile group, a methyl ester group, an ethyl ester group, a hydroxyethyl ester group or a hydroxypropyl ester group.
  • R 5 is hydrogen or methyl.
  • a, b, c, d, and e are independently integers from 0 to 10,000,000, for example, a, b, c, d, and e may independently be 1, 3, 5, 8, 10, 20, 40 , 60, 80, 100, 200, 400, 600, 800, 1000, 2000, 5000, 7000, 9000, 12000, 15000, 18000, 20000, 30000, 50000, 80000, 100000, 300000, 500000, 800000, 1000000, 3000000 5, 8000000, and the specific point values between the above values, limited to the length and for the sake of brevity, the present disclosure will not exhaustively enumerate the specific point values included in the range, and b and c are not 0 at the same time.
  • a, b, c, d and e are independently an integer from 100 to 10,000.
  • f is an integer from 0 to 10000000, for example, f may be 0, 1, 3, 5, 8, 10, 20, 40, 60, 80, 100, 200, 400, 600, 800, 1000, 2000 , 5000, 7000, 9000, 12000, 15000, 18000, 20000, 30000, 50000, 80000, 100000, 300000, 500000, 800000, 1000000, 3000000, 5000000, 8000000, and the specific point value between the above values, limited by space and For the sake of brevity, the present disclosure is not exhaustive of the specific point values included in the scope.
  • f is an integer from 100 to 10,000.
  • b/a 0.05-0.5 (for example, may be 0.05, 0.06, 0.08, 0.1, 0.2, 0.3, 0.4 or 0.5)
  • c/a 0.05-0.5 (for example, may be 0.05, 0.06, 0.08, 0.1, 0.2, 0.3, 0.4 or 0.5)
  • d/a 0.05-0.5 (for example, may be 0.05, 0.06, 0.08, 0.1, 0.2, 0.3, 0.4 or 0.5).
  • the aqueous binder is one or a combination of at least two of the polymers having the structure shown by the following formula A-C:
  • a, b, c, d and e are independently an integer of preferably from 100 to 10,000, and f is an integer of from 0 to 10,000,000, preferably an integer of from 100 to 10,000.
  • the aqueous binder of the lithium ion battery has a solid content of 1-90%, for example, 1%, 3%, 5%, 8%, 10%, 13%, 15%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% or 90%, preferably 5-50%.
  • the viscosity of the aqueous binder for a lithium ion battery is from 1 to 100,000 mPa ⁇ s, for example, 3 mPa ⁇ s, 5 mPa ⁇ s, 8 mPa ⁇ s, 10 mPa ⁇ s, 30 mPa ⁇ s, 50 mPa ⁇ s, and 80 mPa ⁇ s.
  • the viscosity of the aqueous binder for a lithium ion battery is from 100 to 100,000 mPa ⁇ s.
  • the present disclosure provides a method of preparing an aqueous binder for a lithium ion battery as described above, characterized in that the method comprises the steps of:
  • a water-soluble polymer having a hydroxyl group represented by Formula II is reacted with Compound A and Compound B in an aqueous solution of a basic substance to obtain a modified water-soluble polymer represented by Formula III, and the reaction formula is as follows:
  • R 6 is H or a C1-C4 linear alkylene group or a branched alkylene group
  • the M group is a repeating unit group of a water-soluble polymer containing a hydroxyl group or a hydroxyl group and a carboxyl group
  • R 1 is a C1-C6 linear alkylene group or Branched alkylene
  • R 2 is amino, hydroxy, alkoxy, hydroxyalkyl or R is a C1-C6 linear alkylene group or a branched alkylene group
  • R 3 is a phenyl group or a C1-C6 linear alkyl group or a branched alkyl group
  • R 4 is a carboxyl group, an amide group, a nitrile group,
  • R ' is C1-C6 straight chain alkyl or branched alkyl
  • R 5 is hydrogen or a straight-chain alkyl group of C1-C6
  • the hydroxyl group-containing water-soluble polymer is selected from any one or a combination of at least two of starch, vegetable gum, animal glue, cellulose, seaweed gum or polyvinyl alcohol.
  • the hydroxyl group-containing water-soluble polymer has a degree of polymerization of 100 to 10,000,000, for example, 100, 130, 150, 180, 200, 300, 400, 500, 600, 800, 1000, 1300, 1500, 1800, 2000. , 5000, 8000, 10000, 15000, 20000, 40000, 60000, 80000, 100000, 200000, 500000, 800000, 1000000, 1500000, 2000000, 5000000, 8000000 or 10000000, and the specific point value between the above values, limited by space and For the sake of brevity, the present disclosure is not exhaustive of the specific point values included in the scope.
  • the hydroxyl group-containing water-soluble polymer has a polymerization degree of an integer of from 1,000 to 100,000.
  • the basic substance in the step (1) is any one of a basic salt, an inorganic strong base, an inorganic weak base, an organic strong base or an organic weak base, or a combination of at least two.
  • the basic salt is any one or a combination of at least two of a carbonate, a silicate or an acetate.
  • the inorganic strong base is sodium hydroxide and/or lithium hydroxide.
  • the inorganic weak base is aqueous ammonia.
  • the organic strong base is methylamine.
  • the organic weak base is urea and/or pyridine.
  • the mass fraction of the aqueous solution of the basic substance is from 0.1% to 90%, such as 0.01%, 0.05%, 0.08%, 1%, 3%, 5%, 8%, 10%, 20%, 30%. 40%, 50%, 60%, 70%, 80%, 90% or 95%, etc., preferably 1-30%, further preferably 5-20%.
  • the compound A in the step (1) is used in an amount of 0.01% to 99%, such as 0.01%, 0.05%, 0.08%, 1%, 3%, 5%, of the number of moles of the water-soluble polymer repeating unit M. 8%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or 95%, etc., preferably 5-40%.
  • the compound B in the step (1) is used in an amount of 0.01% to 99%, such as 0.01%, 0.05%, 0.08%, 1%, 3%, 5%, of the number of moles of the water-soluble polymer repeating unit M. 8%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or 95%, etc., preferably 5-40%.
  • the medium of the reaction in the step (1) is water.
  • the temperature of the reaction in the step (1) is 30-90 ° C, for example, 30 ° C, 35 ° C, 40 ° C, 45 ° C, 50 ° C, 55 ° C, 60 ° C, 65 ° C, 70 ° C, 75 ° C, 80 °C, 85 ° C or 90 ° C.
  • the reaction time in the step (1) is 0.5-10 hours, for example 0.5 hours, 0.8 hours, 1 hour, 1.3 hours, 1.5 hours, 1.8 hours, 2 hours, 3 hours, 4 hours, 5 hours, 6 Hours, 7 hours, 8 hours, 9 hours or 10 hours.
  • the compound D in the step (2) is used in an amount of 0.01% to 99%, such as 0.01%, 0.05%, 0.08%, 1%, 3%, 5%, of the number of moles of the water-soluble polymer repeating unit M. 8%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or 95%, etc., preferably 5-40%.
  • the initiator in the step (2) is any one or a combination of at least two of an organic peroxide initiator, an inorganic peroxide initiator, or a redox initiator.
  • the organic peroxide initiator is benzoyl peroxide and/or methyl ethyl ketone peroxide.
  • the inorganic peroxide initiator is potassium persulfate and/or ammonium persulfate.
  • the redox initiator is a combination of ammonium persulfate and sodium sulfite and/or a combination of potassium persulfate and ferrous chloride.
  • the initiator is used in an amount of 0.01% to 99%, such as 0.01%, 0.05%, 0.08%, 1%, 3%, 5%, 8%, 10, of the number of moles of the water-soluble polymer repeating unit M. %, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or 95%, etc., preferably 0.1-10%.
  • the compound D in the step (2) is selected from any one of an ethylenically unsaturated carboxylic acid monomer, an acrylate monomer, a methacrylate monomer or a nitrile group-containing olefin monomer or A combination of at least two.
  • the solvent used in the polymerization reaction in the step (2) is water.
  • the temperature of the polymerization reaction in the step (2) is 0-100 ° C, such as 0 ° C, 10 ° C, 20 ° C, 30 ° C, 40 ° C, 50 ° C, 60 ° C, 70 ° C, 80 ° C, 90 ° C or 100 ° C, preferably 30-80 ° C.
  • the polymerization reaction in the step (2) is carried out for 1 to 20 hours, for example, 1 hour, 3 hours, 5 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours or 20 hours.
  • the present disclosure provides a lithium ion battery pole piece comprising an electrode material and an aqueous binder for a lithium ion battery as described above.
  • the battery pole piece is a positive pole piece and/or a negative pole piece.
  • the mass percentage of the aqueous binder for the lithium ion battery in the lithium ion battery pole piece is 1-5%, such as 1%, 1.3%, 1.5%, 1.8%, 2%, 2.3%, 2.5%. 2.8%, 3%, 3.5%, 3.8%, 4%, 4.3%, 4.5%, 4.8% or 5%, preferably 1-3%.
  • a positive electrode tab of a lithium ion battery which comprises the above-mentioned aqueous binder for a lithium ion battery and a positive electrode material, and the aqueous binder of the lithium ion battery is used in a positive electrode tab of a lithium ion battery.
  • the mass percentage is 1-5%, preferably 1-3%.
  • a negative electrode plate for a lithium ion battery comprising the aqueous binder and a negative electrode material for a lithium ion battery as described above, wherein the mass percentage of the aqueous binder for the lithium ion battery in the negative electrode tab of the lithium ion battery is 1 - 5%, preferably 1-3%.
  • the present disclosure adopts a method for chemically modifying a hydroxyl group of a water-soluble polymer to obtain the aqueous binder, which is safe, environmentally friendly, and low in cost, and is suitable for the manufacture of a positive electrode and a negative electrode tab of a lithium ion battery.
  • the structure of the aqueous binder of the present disclosure contains a large amount of anionic groups, which can improve the dispersion effect of the slurry, form a good conductive network of the electrode, and contain a large number of polar groups such as hydroxyl groups and carboxyl groups, which can enhance the polymer and the set.
  • the polarity of the fluid acts to increase adhesion.
  • the binder of the present disclosure is an aqueous binder.
  • the reaction steps involved in the present disclosure are simple, mild, and easy to obtain raw materials, and have good promotion and application value.
  • Example 1 is an infrared contrast spectrum of an aqueous binder for a lithium ion battery obtained from Example 1 of the present disclosure and a raw material polyvinyl alcohol.
  • Figure 1 is an infrared contrast spectrum of an aqueous binder obtained from Example 1 of the present disclosure and a raw material polyvinyl alcohol.
  • the product of Example 1 symmetric stretching vibration of the carboxyl group salt significant peak at 1409cm -1, 1566cm -1 significant vibrational peak with an amide group at 1664cm -1, 1087cm -1 have at A distinct vibrational peak of the COC bond.
  • Example 2 the water-soluble polymer polyvinyl alcohol was replaced with sodium alginate.
  • Example 2 Unlike Example 1, the basic compound lithium silicate was replaced with ethylenediamine.
  • Example 2 Unlike Example 1, the compound A acrylamide was replaced with methacrylamide.
  • Example 2 Unlike Example 1, the compound A acrylamide was replaced with methyl acrylate.
  • Example 2 In contrast to Example 1, the initiator ammonium persulfate was replaced with azobisisobutylphosphonium hydrochloride.
  • a commercially available styrene-butadiene rubber SBR was used as a binder in combination with sodium carboxymethylcellulose (CMC) having a mass ratio of 1:1.
  • CMC carboxymethylcellulose
  • a commercially available acrylic resin PAA was used as a binder.
  • the binder prepared in Examples 1-14 and Comparative Examples 1-2 was used as a positive electrode material and a negative electrode material binder to prepare a positive electrode tab and a negative electrode tab, as follows:
  • positive electrode tab a mass fraction of 93.0% with lithium iron phosphate as a positive electrode material, 4.0% of a conductive additive, and a binder prepared in an example or a comparative example with a mass fraction of 3% by mass, according to total solids A proportion of 65% of the components was added with a proper amount of deionized water to prepare a battery pole piece slurry. The uniformly dispersed slurry was passed through a 100-mesh sieve, coated on a 10 ⁇ m-thick aluminum foil as a current collector, dried at 120 ° C for 5 minutes, and then rolled at a room temperature of 10 ⁇ 10 4 N/m to obtain a positive electrode. Polar film. The properties of the prepared positive electrode tabs were tested and the results are shown in Table 1.
  • negative electrode pole piece the mass fraction of the silicon carbon composite material as the negative electrode material is 96.0%, the conductive additive is 1.0%, and the binder prepared in the example or the comparative example with a solid content of 3% by mass, according to the total
  • a solid electrode slurry was prepared by adding an appropriate amount of deionized water to a solid content of 45%. The uniformly dispersed slurry was passed through a 100 mesh screen, coated on a 10 ⁇ m thick copper foil as a current collector, dried at 120 ° C for 5 minutes, and then rolled at a room temperature of 10 ⁇ 10 4 N/m. Negative pole piece. The properties of the prepared negative electrode tabs were tested, and the results are shown in Table 2.
  • the performance measurement method is as follows:
  • Peel strength was measured: the electrode sheets of the examples and the comparative examples were cut into strips of 10 cm ⁇ 2 cm, and a steel plate having a thickness of 1 mm was bonded to the collector side with a double-sided tape, and a transparent tape was attached to the side of the coating layer.
  • the tensile tester was peeled off at a speed of 100 mm/min toward the 180° direction, and the peeling stress was measured.
  • the battery performance of the positive electrode was measured: the above positive electrode piece was fabricated into an analog battery and the first coulombic efficiency of the charge and discharge cycle was tested by a constant current method.
  • the battery performance of the negative electrode was measured: the above-mentioned negative electrode piece was fabricated into a button cell, and the first coulombic efficiency of the charge and discharge cycle and the capacity retention rate after 50 cycles of the cycle were tested by a constant current method, and the lithium piece was inserted after 50 cycles of the charge and discharge cycle.
  • the ratio of the thickness increase value of the pole piece to the thickness of the pole piece before charging and discharging in the state is recorded as the pole piece expansion ratio.
  • the positive electrode using the binder according to Examples 1 to 14 of the present disclosure has a strong adhesion to the aluminum foil and a good flexibility of the pole piece as compared with the positive electrode using the adhesive of Comparative Example 1-2.
  • the negative electrode using the binder according to Examples 1 to 14 of the present disclosure has strong adhesion to the copper foil and pole piece flexibility as compared with the negative electrode using the binder of Comparative Example 1-2. Good, the first Coulomb efficiency, high capacity retention rate, and small cycle expansion rate.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

本文提供一种锂离子电池用水性粘结剂及其制备方法和锂离子电池极片，所述水性粘结剂具有式I所示的结构，本文通过对水溶性聚合物重复单元基团中的羟基进行修饰以达到引入含有极性阴离子基团的柔性侧链极性基团可以增强聚合物与集流体的极性作用，从而提高粘结力，此外提高了聚合物的柔顺性，从而能够制得柔韧性好的电池极片，并且能够使得电极极片具有高的首次库伦效率。本文的水性粘结剂的制备方法简单，条件温和、原料易得，适合于推广应用。

Description

一种锂离子电池用水性粘结剂及其制备方法和锂离子电池极片 技术领域
本公开属于锂离子电池材料领域，涉及一种锂离子电池用水性粘结剂及其制备方法和锂离子电池极片。
背景技术
如今，锂离子电池已广泛应用于手机、电脑和电动车等产品，具有极大的商业价值。目前商品化锂离子电池的正极材料以氧化物如LiCoO 2、LiMn 2O 4和LiFePO 4等为主；负极材料以石墨为主，由于石墨理论容量较低(372mAh/g)，已经很难满足当今电子信息、能源技术飞速发展的需要，因此开发高容量硅基材料(理论容量4200mAh/g)成为锂离子电池技术发展的重大课题。然而，由于硅基材料在充放电时伴随着更大的体积膨胀和收缩(最高可达300％)，导致电极容量衰减快，循环性能差。因此，需要开发高粘结强度和能够均匀分散膨胀应力的粘结剂来实现高容量负极的循环稳定性。
现今锂离子电池领域最常用的粘结剂有聚偏氟乙烯(PVDF)、苯乙烯-丁二烯橡胶(SBR)和丙烯酸类聚合物(PAA)。采用PVDF作为粘结剂，溶解PVDF所用到的有机溶剂如氮甲基吡咯烷酮(NMP)对环境和人体有害，且价格昂贵。采用SBR作为粘结剂，必须同时添加纤维素(CMC)作为增稠剂，但CMC粘性一般，且脆性大、柔顺差，充放电时极片易龟裂。同时，SBR粘结剂为点-点粘结机理应用于硅基复合新型负极时，因充放电循环时硅基体积膨胀大，点粘结极易失去粘结性，使得电性能劣化。采用PAA作为粘结剂，由于该聚合物玻璃化转变温度高，在常温下较硬，易导致极片硬、脆，因此，该粘结剂在涂布过程中易出现开裂现象、冷压后出现许多条纹、裁片时边缘脱碳以及卷绕过程 中极片弯折处掉粉的现象，加工性能差，从而严重制约了其在电池中的应用。
CN104356979A公开了一种用于锂离子电池电极材料的聚丙烯酸酯类水性粘结剂、制备方法及锂离子电池极片，该粘结剂为一种交联型高固含量的聚丙烯酸酯类水性粘结剂，此粘结剂聚合物分子链段由亲水性链段和亲油性链段两部分组成，并经交联剂交联成空间网状结构。用此粘结剂制作的电极极片在充放电过程中不会出现“掉料”现象，且对锂离子电池正、负极电极材料均具有较好的粘结性能，可抑制石墨负极类材料的极片膨胀，特别是抑制硅基材料的极片膨胀。
通过对粘结剂的改进，可以在具备较好粘结性的基础上，提高极片的性能，因此在本领域期望能够开发出更多具备良好性能的锂离子电池用粘结剂。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
本公开的目的在于提供一种锂离子电池用水性粘结剂及其制备方法和锂离子电池极片。本公开的粘结剂具有较高的粘结力，使得电池极片与铝箔粘结力强、极片柔韧性好、首次库伦效率高。
为达到本公开目的，本公开采用以下技术方案：
一方面，本公开提供一种锂离子电池用水性粘结剂，所述水性粘结剂具有式I所示的结构：
Figure PCTCN2018077446-appb-000001
其中M基团为含有羟基或含有羟基和羧基的水溶性聚合物的重复单元基团，R 1为C1-C6的直链亚烷基或支链亚烷基；R 2为氨基、羟基、烷氧基、羟基烷基或
Figure PCTCN2018077446-appb-000002
R为C1-C6的直链亚烷基或支链亚烷基；R 3为苯基或C1-C6的直链烷基或支链烷基，R 4为羧基、酰胺基、腈基、
Figure PCTCN2018077446-appb-000003
其中R′为C1-C6的直链烷基或支链烷基，R″为C1-C6的直链亚烷基或支链亚烷基；R 5为氢或C1-C6的直链烷基或支链烷基，a、b、c、d和e独立地为1-10000000的整数，b和c不同时为0，f为0-10000000的整数。
由本公开的式I可以看出，本公开是对水溶性聚合物重复单元基团中的羟基进行修饰以达到引入含有极性阴离子基团的柔性侧链极性基团可以增强聚合物与集流体的极性作用，从而提高粘结力；阴离子基团可以在浆料分散时吸附在颗粒表面，提高颗粒间的静电斥力，从而改善电极浆料的分散效果；柔性侧链可以破坏原有分子链的规整性，减弱聚合物链间的氢键作用，从而减弱结晶；柔性侧链还可以降低聚合物的玻璃化转变温度，从而增强柔顺性。
优选地，所述M基团为来自以下结构中的重复单元基团：
Figure PCTCN2018077446-appb-000004
Figure PCTCN2018077446-appb-000005
中的任意一种。
即本公开的水性粘结剂中主链由
Figure PCTCN2018077446-appb-000006
Figure PCTCN2018077446-appb-000007
Figure PCTCN2018077446-appb-000008
中的任意一种构成，例如当M基团为来自
Figure PCTCN2018077446-appb-000009
结构中的重复单元基团时，即本公开的水性粘结剂主链以
Figure PCTCN2018077446-appb-000010
基团为重复单元，通过对其中含有的羟基进行修饰得到如上式I所示的结构，其中有些链段的羟基被修饰，但是有些没有被修饰，还保留一部分带有羟基的重复单元链段，而此时结构中不含有羧基，f＝0；又如当M基团为来自
Figure PCTCN2018077446-appb-000011
结构中的重复单元基团时，即本公开的水性粘结剂主链以
Figure PCTCN2018077446-appb-000012
基团为重复单元，对其中含有的羟基进行修饰得到如上式I所示的结构，其中有些链段的羟基被修饰，但是有些没有被修饰，还保留一部分带有羟基的重复单元链段，羟基被修饰的链段中可能是一个重复单元中的一个羟基被修饰也可能是多个羟基被修饰；此时
Figure PCTCN2018077446-appb-000013
均表示未被修饰的链段。
在本公开中，所述C1-C6的直链亚烷基或支链亚烷基可以为C1、C2、C3、C4、C5、C6的直链亚烷基或支链亚烷基，例如可以为-CH 2-、-CH 2CH 2-或
Figure PCTCN2018077446-appb-000014
等。
在本公开中，所述C1-C6的直链烷基或支链烷基可以为C1、C2、C3、C4、C5、C6的直链烷基或支链烷基，例如可以为甲基、乙基或
Figure PCTCN2018077446-appb-000015
等。
在本公开中，所述烷氧基可以为甲氧基、乙氧基或丙氧基等。
在本公开中，所述羟基烷基可以为羟乙基、羟丙基、羟丁基等。
优选地，R 1为-CH 2CH 2-或
Figure PCTCN2018077446-appb-000016
优选地，R 2为氨基、羟基、甲氧基、羟乙基、羟丙基、
Figure PCTCN2018077446-appb-000017
Figure PCTCN2018077446-appb-000018
优选地，R 3为苯基或甲基。
优选地，R 4为羧基、酰胺基、腈基、甲酯基、乙酯基、羟乙酯基或羟丙酯基。
优选地，R 5为氢或甲基。
在本公开中，a、b、c、d和e独立地为0-10000000的整数，例如a、b、c、d和e可独立地为1、3、5、8、10、20、40、60、80、100、200、400、600、800、1000、2000、5000、7000、9000、12000、15000、18000、20000、30000、50000、80000、100000、300000、500000、800000、1000000、3000000、5000000、8000000，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本公开不再穷尽列举所述范围包括的具体点值，且b和c不同时为0。优选地，a、b、c、d和e独立地为100-10000的整数。
在本公开中，f为0-10000000的整数，例如f可以为0、1、3、5、8、10、20、40、60、80、100、200、400、600、800、1000、2000、5000、7000、9000、12000、15000、18000、20000、30000、50000、80000、100000、300000、500000、800000、1000000、3000000、5000000、8000000，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本公开不再穷尽列举所述范围包括的具体点值。优选地，f为100-10000的整数。
优选地，b/a＝0.05-0.5(例如可以为0.05、0.06、0.08、0.1、0.2、0.3、0.4或0.5)，c/a＝0.05-0.5(例如可以为0.05、0.06、0.08、0.1、0.2、0.3、0.4或0.5)，d/a＝0.05-0.5(例如可以为0.05、0.06、0.08、0.1、0.2、0.3、0.4或0.5)。
优选地，所述水性粘结剂为具有如下式A-C所示结构的聚合物中的一种或 至少两种的组合：
Figure PCTCN2018077446-appb-000019
其中a、b、c、d和e独立地为优选为100-10000的整数，f为0-10000000的整数，优选为100-10000的整数。
优选地，所述锂离子电池用水性粘结剂的固含量为1-90％，例如1％、3％、5％、8％、10％、13％、15％、18％、20％、25％、30％、35％、40％、45％、50％、55％、60％、65％、70％、75％、80％、85％或90％，优选5-50％。
优选地，所述锂离子电池用水性粘结剂的粘度为1-100000mPa·s，例如3mPa·s、5mPa·s、8mPa·s、10mPa·s、30mPa·s、50mPa·s、80mPa·s、100mPa ·s、200mPa·s、500mPa·s、1000mPa·s、2000mPa·s、5000mPa·s、8000mPa·s、10000mPa·s、30000mPa·s、50000mPa·s、80000mPa·s或90000mPa·s，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本公开不再穷尽列举所述范围包括的具体点值。优选地，锂离子电池用水性粘结剂的粘度为100-100000mPa·s。
另一方面，本公开提供如上所述锂离子电池用水性粘结剂的制备方法，其特征在于，所述方法包括以下步骤：
(1)使式II所示含有羟基的水溶性聚合物在碱性物质的水溶液中与化合物A和化合物B进行反应，得到式III所示修饰后的水溶性聚合物，反应式如下：
Figure PCTCN2018077446-appb-000020
其中R 6为H或C1-C4的直链亚烷基或支链亚烷基；
(2)式III所示修饰后的水溶性聚合物与化合物D在引发剂作用下发生聚合反应，得到式I所示锂离子电池用水性粘结剂，反应式如下：
Figure PCTCN2018077446-appb-000021
如上所述反应式中基团的限定如上所述，即M基团为含有羟基或含有羟基和羧基的水溶性聚合物的重复单元基团，R 1为C1-C6的直链亚烷基或支链亚烷基；R 2为氨基、羟基、烷氧基、羟基烷基或
Figure PCTCN2018077446-appb-000022
R为C1-C6的直链亚烷基或支链亚烷基；R 3为苯基或C1-C6的直链烷基或支链烷基，R 4为羧基、酰胺基、腈基、
Figure PCTCN2018077446-appb-000023
其中R′为C1-C6的直链烷基或支链烷基，R″为C1-C6的直链亚烷基或支链亚烷基；R 5为氢或C1-C6的直链烷基或支链烷基，a、b、c、d和e独立地为1-10000000的整数，f为0-10000000的整数。
优选地，所述含有羟基的水溶性聚合物选自淀粉类、植物胶、动物胶、纤维素、海藻胶或聚乙烯醇中的任意一种或至少两种的组合。
优选地，所述含有羟基的水溶性聚合物的聚合度为100-10000000，例如100、130、150、180、200、300、400、500、600、800、1000、1300、1500、1800、2000、5000、8000、10000、15000、20000、40000、60000、80000、100000、200000、500000、800000、1000000、1500000、2000000、5000000、8000000或10000000，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本公 开不再穷尽列举所述范围包括的具体点值。优选地，所述含有羟基的水溶性聚合物的聚合度为1000-100000的整数。
优选地，步骤(1)所述碱性物质为碱性盐类、无机强碱、无机弱碱、有机强碱或有机弱碱中的任意一种或至少两种的组合。
优选地，所述碱性盐类为碳酸盐、硅酸盐或醋酸盐中的任意一种或至少两种的组合。
优选地，所述无机强碱为氢氧化钠和/或氢氧化锂。
优选地，所述无机弱碱为氨水。
优选地，所述有机强碱为甲胺。
优选地，所述有机弱碱为尿素和/或吡啶。
优选地，所述碱性物质的水溶液的质量分数为0.1％-90％，例如0.01％、0.05％、0.08％、1％、3％、5％、8％、10％、20％、30％、40％、50％、60％、70％、80％、90％或95％等，优选1-30％，进一步优选5-20％。
优选地，步骤(1)所述化合物A的用量为水溶性聚合物重复单元M的摩尔数的0.01％-99％，例如0.01％、0.05％、0.08％、1％、3％、5％、8％、10％、20％、30％、40％、50％、60％、70％、80％、90％或95％等，优选5-40％。
优选地，步骤(1)所述化合物B的用量为水溶性聚合物重复单元M的摩尔数的0.01％-99％，例如0.01％、0.05％、0.08％、1％、3％、5％、8％、10％、20％、30％、40％、50％、60％、70％、80％、90％或95％等，优选5-40％。
优选地，步骤(1)所述反应的介质为水。
优选地，步骤(1)所述反应的温度为30-90℃，例如30℃、35℃、40℃、45℃、50℃、55℃、60℃、65℃、70℃、75℃、80℃、85℃或90℃。
优选地，步骤(1)所述反应的时间为0.5-10小时，例如0.5小时、0.8小时、 1小时、1.3小时、1.5小时、1.8小时、2小时、3小时、4小时、5小时、6小时、7小时、8小时、9小时或10小时。
优选地，步骤(2)所述化合物D的用量为水溶性聚合物重复单元M的摩尔数的0.01％-99％，例如0.01％、0.05％、0.08％、1％、3％、5％、8％、10％、20％、30％、40％、50％、60％、70％、80％、90％或95％等，优选5-40％。
优选地，步骤(2)所述引发剂为有机过氧化物引发剂、无机过氧化物引发剂，或者氧化还原引发剂中的任意一种或至少两种的组合。
优选地，所述有机过氧化物引发剂为过氧化苯甲酰和/或过氧化甲乙酮。
优选地，所述无机过氧化物引发剂为过硫酸钾和/或过硫酸铵。
优选地，所述氧化还原引发剂为过硫酸铵与亚硫酸钠的组合和/或过硫酸钾与氯化亚铁的组合。
优选地，所述引发剂的用量为水溶性聚合物重复单元M的摩尔数的0.01％-99％，例如0.01％、0.05％、0.08％、1％、3％、5％、8％、10％、20％、30％、40％、50％、60％、70％、80％、90％或95％等，优选0.1-10％。
优选地，步骤(2)所述化合物D选自烯类不饱和羧酸单体、丙烯酸酯类单体、甲基丙烯酸酯类单体或含腈基的烯烃类单体中的任意一种或至少两种的组合。
优选地，步骤(2)所述聚合反应中所用溶剂为水。
优选地，步骤(2)所述聚合反应的温度为0-100℃，例如0℃、10℃、20℃、30℃、40℃、50℃、60℃、70℃、80℃、90℃或100℃，优选30-80℃。
优选地，步骤(2)所述聚合反应的时间为1-20小时，例如1小时、3小时、5小时、8小时、10小时、12小时、14小时、16小时、18小时或20小时。
另一方面，本公开提供了一种锂离子电池极片，所述锂离子电池极片包含 电极材料和如上所述的锂离子电池用水性粘结剂。
优选地，所述电池极片为正极极片和/或负极极片。
优选地，所述锂离子电池用水性粘结剂在锂离子电池极片中的质量百分比为1-5％，例如1％、1.3％、1.5％、1.8％、2％、2.3％、2.5％、2.8％、3％、3.5％、3.8％、4％、4.3％、4.5％、4.8％或5％，优选1-3％。
具体地为：一种锂离子电池正极极片，其包含如上所述的锂离子电池用水性粘结剂和正极材料，所述锂离子电池用水性粘结剂在锂离子电池正极极片中的质量百分比为1-5％，优选1-3％。
一种锂离子电池负极极片，其包含如上所述的锂离子电池用水性粘结剂和负极材料，所述锂离子电池用水性粘结剂在锂离子电池负极极片中的质量百分比为1-5％，优选1-3％。
与现有技术相比，本公开具有以下有益效果：
本公开采用对水溶性聚合物的羟基进行化学修饰的方法得到所述水性粘结剂，安全环保、成本低，适用于锂离子电池正极和负极极片的制造。本公开的水性粘结剂的结构中含有大量的阴离子基团，可以提高浆料分散效果，使电极形成良好的导电网络，含有大量的羟基、羧基等极性基团，可以增强聚合物与集流体的极性作用，从而提高粘结力。通过将羟基进行烷基化，实现在主链上引入柔性侧链的结构，提高了聚合物的柔顺性，从而制得柔韧性好的电池极片。本公开的粘结剂属于水性粘结剂。本公开所涉及到的反应步骤简单、条件温和、原料易得，具有很好的推广和应用价值。
附图说明
图1为本公开实施例1得到的锂离子电池用水性粘结剂与原料聚乙烯醇的红外对比谱图。
具体实施方式
下面通过具体实施方式来进一步说明本公开的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本公开，不应视为对本公开的具体限制。
实施例1
将80g聚乙烯醇(重复单元M的摩尔数为1.82mol)加入到500g质量分数为2％的硅酸锂的水溶液当中，40℃搅拌2小时，然后升温至60℃，加入50g质量分数为60％的丙烯酰胺水溶液反应，保温反应4小时，然后降温至50℃，加入4g质量分数为0.1％的过硫酸铵水溶液和40g质量分数为50％的丙烯酸水溶液，保温反应5h，得到粘稠液体，即为水性粘结剂。
图1是本公开实施例1得到的水性粘结剂与原料聚乙烯醇的红外对比谱图。由图1可以看出，实施例1的产品在1409cm -1处有明显的羧基盐的对称伸缩振动峰，1566cm -1与1664cm -1处有明显的酰胺基的振动峰，1087cm -1处有明显的C-O-C键的振动峰。
实施例2
将80g聚乙烯醇(重复单元M的摩尔数为1.82mol)加入到500g质量分数为5％的硅酸锂的水溶液当中，50℃搅拌0.5小时，然后升温至90℃，加入32.3g质量分数为40％的丙烯酰胺水溶液反应，保温反应0.5小时，然后降温至30℃，加入4g质量分数为0.1％的过硫酸铵水溶液和40g质量分数为50％的丙烯酸水溶液，保温反应5h，得到粘稠液体。
实施例3
将80g聚乙烯醇(重复单元M的摩尔数为1.82mol)加入到500g质量分数为10％的硅酸锂的水溶液当中，30℃搅拌2小时，然后升温至90℃，加入86g质量分数为60％的丙烯酰胺水溶液以及10.6g甲基环氧乙烷进行反应，保温反应 4小时，然后降温至80℃，加入4g质量分数为0.1％的过硫酸铵水溶液和40g质量分数为50％的丙烯酸水溶液，保温反应10h，得到粘稠液体，即为水性粘结剂。
实施例4
将80g聚乙烯醇(重复单元M的摩尔数为1.82mol)加入到500g质量分数为10％的硅酸锂的水溶液当中，40℃搅拌2小时，然后升温至80℃，加入42.2g甲基环氧乙烷进行反应，保温反应10小时，然后降温至30℃，加入4g质量分数为0.1％的过硫酸铵水溶液和40g质量分数为50％的丙烯酸水溶液，保温反应15h，得到粘稠液体，即为水性粘结剂。
实施例5
与实施例1不同的是，将水溶性聚合物聚乙烯醇替换为羧甲基纤维素钠。
实施例6
与实施例1不同的是，将水溶性聚合物聚乙烯醇替换为海藻酸钠。
实施例7
与实施例1不同的是，将碱性化合物硅酸锂替换为氢氧化锂。
实施例8
与实施例1不同的是，将碱性化合物硅酸锂替换为乙二胺。
实施例9
与实施例1不同的是，将化合物A丙烯酰胺替换为甲基丙烯酰胺。
实施例10
与实施例1不同的是，将化合物A丙烯酰胺替换为丙烯酸甲酯。
实施例11
与实施例1不同的是，将引发剂过硫酸铵替换为过氧化苯甲酰。
实施例12
与实施例1不同的是，将引发剂过硫酸铵替换为偶氮二异丁脒盐酸盐。
实施例13
与实施例1不同的是，将丙烯酸替换为丙烯酰胺。
实施例14
与实施例1不同的是，将丙烯酸替换为甲基丙烯酸。
对比例1
以某公司市售丁苯橡胶SBR作为粘结剂，配合质量比1∶1的羧甲基纤维素钠(CMC)使用。
对比例2
以某公司市售丙烯酸树脂PAA作为粘结剂。
将实施例1-14以及对比例1-2制备的粘结剂作为正极材料和负极材料粘结剂制作正极极片和负极极片，方法如下：
正极极片的制作：以磷酸铁锂作为正极材料的质量分数为93.0％，导电添加剂4.0％，以固含量计质量分数为3％的实施例或对比例所制备的粘结剂，按照总固体成份为65％的比例加入适量去离子水，制成电池极片浆料。将分散均匀的浆料过100目筛网后，涂布于作为集流体的10μm厚铝箔上，120℃干燥5分钟后，室温下以10×10 4N/m的单位长度载荷压延而获得正极极片。对制备的正极极片的性能进行测试，结果如表1所示。
负极极片的制作：以硅碳复合材料作为负极材料的质量分数为96.0％，导电添加剂1.0％，以固含量计质量分数为3％的实施例或对比例所制备的粘结剂，按照总固体成份为45％的比例加入适量去离子水，制成电池极片浆料。将分散均匀的浆料过100目筛网后，涂布于作为集流体的10μm厚铜箔上，120℃干燥5 分钟后，室温下以10×10 4N/m的单位长度载荷压延而获得负极极片。对制备的负极极片的性能进行测试，结果如表2所示。
性能测定方法如下：
测定剥离强度：将实施例和对比例的电极极片切成10cm×2cm的长条状，在集流体侧用双面胶粘接厚1mm的钢板，在涂布层侧粘贴透明胶带，用拉伸试验机以100mm/min的速度朝180°方向剥离，并测定剥离应力。
测定极片柔韧性：将实施例和对比例的辊压后极片的集流体一侧放置直径Φ＝3mm芯棒，并进行弯折实验，通过光学显微镜观察此时极片的状态，极片完好记为○，发生脱落或者开裂记为×。
测定正极的电池性能：将上述正极极片制作模拟电池并采用恒流法测试其充放电循环的首次库仑效率。
测定负极的电池性能：将上述负极极片制作扣式电池并采用恒流法测试其充放电循环的首次库仑效率和循环50次后的容量保持率，充放电循环50周后，极片嵌锂状态下极片厚度增加值与充放电前极片厚度的比值记为极片膨胀率。
表1
Figure PCTCN2018077446-appb-000024
Figure PCTCN2018077446-appb-000025
从表1看出，与采用对比例1-2的粘合剂的正极相比，采用根据本公开实施例1-14的粘结剂的正极具有与铝箔粘结力强、极片柔韧性好、首次库伦效率高的优点。
表2
Figure PCTCN2018077446-appb-000026
Figure PCTCN2018077446-appb-000027
从表2看出，与采用对比例1-2的粘结剂的负极相比，采用根据本公开实施例1-14的粘结剂的负极具有与铜箔粘结力强、极片柔韧性好、首次库伦效率高、容量保持率高、循环膨胀率小的优点。
申请人声明，以上仅为本发明的较佳实施例，但本发明并不局限于上述实施例，即不意味着本发明必须依赖上述实施例才能实施。所属技术领域的技术人员应该明了，对本公开的任何改进，对本公开所选用原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (12)

  1. 一种锂离子电池用水性粘结剂，所述水性粘结剂具有式I所示的结构：
    Figure PCTCN2018077446-appb-100001
    其中M基团为含有羟基或含有羟基和羧基的水溶性聚合物的重复单元基团，R 1为C1-C6的直链亚烷基或支链亚烷基；R 2为氨基、羟基、烷氧基、羟基烷基或
    Figure PCTCN2018077446-appb-100002
    R为C1-C6的直链亚烷基或支链亚烷基；R 3为苯基或C1-C6的直链烷基或支链烷基，R 4为羧基、酰胺基、腈基、
    Figure PCTCN2018077446-appb-100003
    其中R′为C1-C6的直链烷基或支链烷基，R″为C1-C6的直链亚烷基或支链亚烷基；R 5为氢或C1-C6的直链烷基或支链烷基，a、b、c、d和e独立地为0-10000000的整数，b和c不同时为0，f为0-10000000的整数。
  2. 根据权利要求1所述的锂离子电池用水性粘结剂，其中，所述M基团为来自以下结构中的重复单元基团：
    Figure PCTCN2018077446-appb-100004
    Figure PCTCN2018077446-appb-100005
    中的任意 一种。
  3. 根据权利要求1或2所述的锂离子电池用水性粘结剂，其中，R 1为-CH 2CH 2-或
    Figure PCTCN2018077446-appb-100006
  4. 根据权利要求1-3任一项所述的锂离子电池用水性粘结剂，其中，R 2为氨基、羟基、甲氧基、羟乙基、羟丙基、
    Figure PCTCN2018077446-appb-100007
    优选地，R 3为苯基或甲基；
    优选地，R 4为羧基、酰胺基、腈基、甲酯基、乙酯基、羟乙酯基或羟丙酯基；
    优选地，R 5为氢或甲基；
    优选地，a、b、c、d和e独立地为100-10000的整数；
    优选地，f为100-10000的整数；
    优选地，b/a＝0.05-0.5，c/a＝0.05-0.5，d/a＝0.05-0.5；
    优选地，所述水性粘结剂为具有如下式A-C所示结构的聚合物中的一种或至少两种的组合：
    Figure PCTCN2018077446-appb-100008
    Figure PCTCN2018077446-appb-100009
    其中a、b、c、d和e独立地为0-10000000的整数，优选为100-10000的整数，且b和c不同时为0，f为0-10000000的整数，优选为100-10000的整数。
  5. 根据权利要求1-4任一项所述的锂离子电池用水性粘结剂，其中，所述锂离子电池用水性粘结剂的固含量为1-90％，优选5-50％；
    优选地，所述锂离子电池用水性粘结剂的粘度为1-100000mPa·s，优选100-100000mPa·s。
  6. 根据权利要求1-5中任一项所述的锂离子电池用水性粘结剂的制备方法，所述方法包括以下步骤：
    (1)使式II所示含有羟基的水溶性聚合物在碱性物质的水溶液中与化合物A和/或化合物B进行反应，得到式III所示修饰后的水溶性聚合物，反应式如下：
    Figure PCTCN2018077446-appb-100010
    其中R 6为H或C1-C4的直链亚烷基或支链亚烷基；
    (2)式III所示修饰后的水溶性聚合物与化合物D在引发剂作用下发生聚合反应，得到式I所示锂离子电池用水性粘结剂，反应式如下：
    Figure PCTCN2018077446-appb-100011
  7. 根据权利要求6所述的制备方法，其中，所述含有羟基的水溶性聚合物选自淀粉类、植物胶、动物胶、纤维素、海藻胶或聚乙烯醇中的任意一种或至少两种的组合；
    优选地，所述含有羟基的水溶性聚合物的聚合度为100-10000000，优选100-10000的整数。
  8. 根据权利要求6或7所述的制备方法，其中，步骤(1)所述碱性物质为碱性盐类、无机强碱、无机弱碱、有机强碱或有机弱碱中的任意一种或至少两种的组合；
    优选地，所述碱性盐类为碳酸盐、硅酸盐或醋酸盐中的任意一种或至少两种的组合；
    优选地，所述无机强碱为氢氧化钠和/或氢氧化锂；
    优选地，所述无机弱碱为氨水；
    优选地，所述有机强碱为甲胺；
    优选地，所述有机弱碱为尿素和/或吡啶；
    优选地，所述碱性物质的水溶液的质量分数为0.1％-90％，优选1-30％，进一步优选5-20％。
  9. 根据权利要求6-8中任一项所述的制备方法，其中，步骤(1)所述化合物A的用量为水溶性聚合物重复单元M的摩尔数的0.01％-99％，优选5-40％；
    优选地，步骤(1)所述化合物B的用量为水溶性聚合物重复单元M的摩尔数的0.01％-99％，优选5-40％；
    优选地，步骤(1)所述反应的介质为水；
    优选地，步骤(1)所述反应的温度为30-90℃；
    优选地，步骤(1)所述反应的时间为0.5-10小时。
  10. 根据权利要求6-9中任一项所述的制备方法，其中，步骤(2)所述化合物D的用量为水溶性聚合物重复单元M的摩尔数的0.01％-99％，优选5-40％；
    优选地，步骤(2)所述引发剂为有机过氧化物引发剂、无机过氧化物引发剂或者氧化还原引发剂中的任意一种或至少两种的组合；
    优选地，所述有机过氧化物引发剂为过氧化苯甲酰和/或过氧化甲乙酮；
    优选地，所述无机过氧化物引发剂为过硫酸钾和/或过硫酸铵；
    优选地，所述氧化还原引发剂为过硫酸铵与亚硫酸钠的组合和/或过硫酸钾与氯化亚铁的组合；
    优选地，所述引发剂的用量为水溶性聚合物重复单元M的摩尔数的0.01％-99％，优选0.1-10％；
    优选地，步骤(2)所述化合物D选自烯类不饱和羧酸单体、丙烯酸酯类单体、甲基丙烯酸酯类单体或含腈基的烯烃类单体中的任意一种或至少两种的组合；
    优选地，步骤(2)所述聚合反应中所用溶剂为水；
    优选地，步骤(2)所述聚合反应的温度为0-100℃，优选30-80℃；
    优选地，步骤(2)所述聚合反应的时间为1-20小时。
  11. 一种锂离子电池极片，所述锂离子电池极片包含电极材料和如权利要求1-5中任一项所述的锂离子电池用水性粘结剂。
  12. 根据权利要求11所述的锂离子电池极片，其中，所述电池极片为正极极片和/或负极极片；
    优选地，所述锂离子电池用水性粘结剂在锂离子电池极片中的质量百分比为1-5％，优选1-3％。
PCT/CN2018/077446 2017-03-09 2018-02-27 一种锂离子电池用水性粘结剂及其制备方法和锂离子电池极片 WO2018161822A1 (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020197008899A KR102284520B1 (ko) 2017-03-09 2018-02-27 리튬이온전지용 수성 바인더와 그 제조방법, 및 리튬이온전지 극편
JP2019529311A JP6877545B2 (ja) 2017-03-09 2018-02-27 リチウムイオン二次電池用水性粘着剤、およびその調製方法とリチウムイオン二次電池極板

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201710138795.6 2017-03-09
CN201710138795.6A CN106866846B (zh) 2017-03-09 2017-03-09 一种锂离子电池用水性粘结剂及其制备方法和锂离子电池极片

Publications (1)

Publication Number Publication Date
WO2018161822A1 true WO2018161822A1 (zh) 2018-09-13

Family

ID=59171353

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/077446 WO2018161822A1 (zh) 2017-03-09 2018-02-27 一种锂离子电池用水性粘结剂及其制备方法和锂离子电池极片

Country Status (4)

Country Link
JP (1) JP6877545B2 (zh)
KR (1) KR102284520B1 (zh)
CN (1) CN106866846B (zh)
WO (1) WO2018161822A1 (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114342125A (zh) * 2020-06-17 2022-04-12 广东省皓智科技有限公司 用于二次电池的粘结剂组合物
CN114388795A (zh) * 2021-12-01 2022-04-22 广州理文科技有限公司 锂离子电池硅碳负极粘结剂及其制备方法
CN116875234A (zh) * 2023-07-25 2023-10-13 阿梓萨科技(深圳)有限公司 阴阳离子聚合物复合型电池正极粘结剂的制备方法

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106866846B (zh) * 2017-03-09 2020-09-08 宣城研一新能源科技有限公司 一种锂离子电池用水性粘结剂及其制备方法和锂离子电池极片
KR102211109B1 (ko) * 2017-09-15 2021-02-02 주식회사 엘지화학 실리콘 전극 바인더
CN109585896A (zh) * 2017-09-29 2019-04-05 辉能科技股份有限公司 可挠电池
CN110616055B (zh) * 2018-06-20 2022-08-05 贝特瑞新材料集团股份有限公司 一种水性粘结剂及其制备方法和用途
CN110690451B (zh) * 2018-07-05 2022-09-13 贝特瑞新材料集团股份有限公司 一种锂离子电池用导电水性粘合剂及其制备方法和应用
KR102663020B1 (ko) * 2018-10-12 2024-05-07 삼성전자주식회사 바인더, 그 제조방법, 이를 포함하는 이차전지용 전극 및 이차전지
CN110993882B (zh) * 2019-10-21 2021-04-13 中船重工黄冈水中装备动力有限公司 一种电池极板挂网复合的制备方法
CN112467133B (zh) * 2020-03-30 2022-03-18 万向一二三股份公司 一种锂离子电池负极浆料及其制备方法
CN112159638B (zh) * 2020-08-28 2022-06-03 江苏卓高新材料科技有限公司 一种树枝状水性粘结剂、负电极极片、电池及方法
CN112599878B (zh) * 2020-12-14 2022-04-19 中国科学院福建物质结构研究所 一种电极废料的处理方法及应用
KR20240123331A (ko) * 2021-12-22 2024-08-13 니폰 제온 가부시키가이샤 전고체 이차 전지용 바인더 조성물, 전고체 이차 전지용 슬러리 조성물, 전고체 이차 전지용 기능층 및 전고체 이차 전지
CN114335542B (zh) * 2021-12-31 2024-06-14 湖南高瑞电源材料有限公司 一种改善锂电池负极片开裂的添加剂及其制备方法和应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101260282A (zh) * 2008-03-18 2008-09-10 成都中科来方能源科技有限公司 锂离子电池用水性粘合剂、制备方法及锂离子电池正极片
JP2010177060A (ja) * 2009-01-30 2010-08-12 Hymo Corp 電池負極用バインダー組成物
CN105504169A (zh) * 2016-01-07 2016-04-20 上海交通大学 一种用于锂离子电池的粘结剂
CN105914377A (zh) * 2016-06-28 2016-08-31 中国科学院广州能源研究所 一种多元功能化改性高分子锂离子电池粘结剂及在电化学储能器件中的应用
CN105958075A (zh) * 2016-06-28 2016-09-21 中国科学院广州能源研究所 多元功能化改性聚乙烯醇基锂离子电池水性粘结剂及在电化学储能器件中的应用
CN106866846A (zh) * 2017-03-09 2017-06-20 深圳市贝特瑞新能源材料股份有限公司 一种锂离子电池用水性粘结剂及其制备方法和锂离子电池极片

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5941446B2 (ja) * 1978-07-10 1984-10-06 日澱化学株式会社 澱粉↓−ポリビニルアルコ−ルグラフト共重合体の製法
KR20010025102A (ko) * 1999-03-23 2001-03-26 모치즈키 아키히로 이온도전성 고체고분자용 조성물, 이온도전성 고체고분자전해질, 바인더수지 및 2차전지
CN103400990B (zh) * 2013-07-31 2017-08-01 东莞新能源科技有限公司 一种锂离子电池负极材料用粘接剂及包含该粘接剂的电极的制备方法
JP2016154068A (ja) * 2015-02-20 2016-08-25 三菱レイヨン株式会社 非水二次電池電極用バインダ樹脂、非水二次電池電極用バインダ樹脂組成物、非水二次電池電極用スラリー組成物、非水二次電池用電極、及び非水二次電池

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101260282A (zh) * 2008-03-18 2008-09-10 成都中科来方能源科技有限公司 锂离子电池用水性粘合剂、制备方法及锂离子电池正极片
JP2010177060A (ja) * 2009-01-30 2010-08-12 Hymo Corp 電池負極用バインダー組成物
CN105504169A (zh) * 2016-01-07 2016-04-20 上海交通大学 一种用于锂离子电池的粘结剂
CN105914377A (zh) * 2016-06-28 2016-08-31 中国科学院广州能源研究所 一种多元功能化改性高分子锂离子电池粘结剂及在电化学储能器件中的应用
CN105958075A (zh) * 2016-06-28 2016-09-21 中国科学院广州能源研究所 多元功能化改性聚乙烯醇基锂离子电池水性粘结剂及在电化学储能器件中的应用
CN106866846A (zh) * 2017-03-09 2017-06-20 深圳市贝特瑞新能源材料股份有限公司 一种锂离子电池用水性粘结剂及其制备方法和锂离子电池极片

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114342125A (zh) * 2020-06-17 2022-04-12 广东省皓智科技有限公司 用于二次电池的粘结剂组合物
CN114342125B (zh) * 2020-06-17 2024-04-09 广东省皓智科技有限公司 用于二次电池的粘结剂组合物
CN114388795A (zh) * 2021-12-01 2022-04-22 广州理文科技有限公司 锂离子电池硅碳负极粘结剂及其制备方法
CN114388795B (zh) * 2021-12-01 2024-02-20 广州理文科技有限公司 锂离子电池硅碳负极粘结剂及其制备方法
CN116875234A (zh) * 2023-07-25 2023-10-13 阿梓萨科技(深圳)有限公司 阴阳离子聚合物复合型电池正极粘结剂的制备方法

Also Published As

Publication number Publication date
JP6877545B2 (ja) 2021-05-26
CN106866846B (zh) 2020-09-08
CN106866846A (zh) 2017-06-20
KR102284520B1 (ko) 2021-07-30
KR20190045255A (ko) 2019-05-02
JP2019525445A (ja) 2019-09-05

Similar Documents

Publication Publication Date Title
WO2018161822A1 (zh) 一种锂离子电池用水性粘结剂及其制备方法和锂离子电池极片
WO2018000579A1 (zh) 多元功能化改性高分子锂离子电池粘结剂及在电化学储能器件中的应用
US10777818B2 (en) Aqueous binder for lithium ion battery, preparation method therefor and use thereof
TWI601331B (zh) 鋰離子二次電池電極用黏著劑、漿料、電極、及鋰離子二次電池
WO2019242318A1 (zh) 一种水性粘结剂及其制备方法和用途
CN110690451B (zh) 一种锂离子电池用导电水性粘合剂及其制备方法和应用
WO2019061675A1 (zh) 结合涂布烘干工艺的锂离子电池交联型水性粘结剂的制备方法
WO2011145419A1 (ja) リチウムイオン二次電池電極用バインダー、これら電極用バインダーを用いて得られるスラリー、これらスラリーを用いて得られる電極およびこれら電極を用いて得られるリチウムイオン二次電池
CN111139002A (zh) 锂离子电池水溶型粘接剂及其制备方法、电极极片及电池
WO2018000578A1 (zh) 多元功能化改性聚乙烯醇基锂离子电池水性粘结剂及在电化学储能器件中的应用
CN109957361B (zh) 一种水性粘结剂及二次电池
CN107452938B (zh) 负极片及锂离子电池
KR102254067B1 (ko) 이차전지의 전극용 바인더 및 이의 제조 방법
TW201731147A (zh) 二次電池電極用水系黏合劑組成物、二次電池電極用泥漿、黏合劑、二次電池電極及二次電池
CN112279982B (zh) 一种硅基负极用粘结剂及含有该粘结剂的锂离子电池
JP2016042408A (ja) リチウム二次電池電極用バインダーの製造方法及びリチウム二次電池電極用バインダー
JP2013004229A (ja) リチウム二次電池電極用バインダー、リチウム二次電池電極用バインダーの製造方法、リチウム二次電池電極およびリチウム二次電池
JP2024532034A (ja) 表面に結着剤が結合された負極材料、その調製方法および使用
JP2015099653A (ja) 二次電池電極組成物、二次電池電極および二次電池
CN111916740B (zh) 一种聚不饱和羧酸基可控交联型粘结剂及含有该粘结剂的锂离子电池
CN111525132B (zh) 电极用粘合剂树脂、二次电池用阴极及含其的锂二次电池
TWI710581B (zh) 羧甲基纖維素接枝共聚物及其用途
CN108054386A (zh) 一种锂离子电池正极片及制作方法和锂离子电池
KR102401576B1 (ko) 이차전지의 전극용 바인더 수지 및 리튬 이차전지
TWI719913B (zh) 正負極電極材料及其製備方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18763824

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019529311

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20197008899

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18763824

Country of ref document: EP

Kind code of ref document: A1